EP1599764A2 - Method for producing resist substrates - Google Patents
Method for producing resist substratesInfo
- Publication number
- EP1599764A2 EP1599764A2 EP04713886A EP04713886A EP1599764A2 EP 1599764 A2 EP1599764 A2 EP 1599764A2 EP 04713886 A EP04713886 A EP 04713886A EP 04713886 A EP04713886 A EP 04713886A EP 1599764 A2 EP1599764 A2 EP 1599764A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- resist layer
- resist
- layer
- conductive layer
- exposure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000010894 electron beam technology Methods 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 21
- 229920002120 photoresistant polymer Polymers 0.000 claims description 42
- 230000003287 optical effect Effects 0.000 claims description 23
- 238000004049 embossing Methods 0.000 claims description 14
- 230000005670 electromagnetic radiation Effects 0.000 claims description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims 2
- 239000000956 alloy Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 12
- 230000005855 radiation Effects 0.000 description 21
- 238000011161 development Methods 0.000 description 17
- 238000005530 etching Methods 0.000 description 5
- 238000000609 electron-beam lithography Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001093 holography Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K19/08—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means
- G06K19/10—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means at least one kind of marking being used for authentication, e.g. of credit or identity cards
- G06K19/16—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means at least one kind of marking being used for authentication, e.g. of credit or identity cards the marking being a hologram or diffraction grating
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1847—Manufacturing methods
- G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2059—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a scanning corpuscular radiation beam, e.g. an electron beam
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2059—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a scanning corpuscular radiation beam, e.g. an electron beam
- G03F7/2061—Electron scattering (proximity) correction or prevention methods
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H1/024—Hologram nature or properties
- G03H1/0244—Surface relief holograms
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/04—Processes or apparatus for producing holograms
- G03H1/08—Synthesising holograms, i.e. holograms synthesized from objects or objects from holograms
- G03H1/0891—Processes or apparatus adapted to convert digital holographic data into a hologram
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/04—Processes or apparatus for producing holograms
- G03H1/0476—Holographic printer
- G03H2001/0478—Serial printer, i.e. point oriented processing
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2224/00—Writing means other than actinic light wave
- G03H2224/04—Particle beam, e.g. e-beam
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2260/00—Recording materials or recording processes
- G03H2260/14—Photoresist
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2260/00—Recording materials or recording processes
- G03H2260/50—Reactivity or recording processes
- G03H2260/63—Indirect etching, e.g. lithography
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/143—Electron beam
Definitions
- the invention relates to a method for producing a substrate having a resist layer in the form of a relief structure, which represents a diffraction structure, wherein the substrate has a conductive layer which scatters the primary electrons when exposing the resist layer by means of an electron beam and / or generates secondary electrons.
- the invention further relates to a resist master and a resist substrate.
- Optically variable elements which have optical properties varying with the viewing angle are frequently used as counterfeit or copy protection for value documents, such as credit cards, bank notes or the like, but also for product protection on any product packages.
- the optically variable elements have the diffraction structure of a true hologram, computer hologram or the diffraction structure of a lattice image with lattice fields arranged next to one another.
- a hologram is a superposition of diffraction gratings.
- a grating image is composed of a multiplicity of grid fields arranged side by side, each of which has a uniform diffraction grating.
- the diffraction gratings of the different grating fields may differ with regard to the grating constant or the azimuth angle or the contour or the outline of the image area occupied by the respective diffraction grating.
- the lattice constant corresponds to the spacing of the grid lines and is essential for the color of the respective image region in the lattice image which can be recognized at a certain viewing angle.
- the azimuth angle describes the inclination of the grid lines with respect to a reference direction and is responsible for the visibility of the image areas in certain viewing directions.
- optically varia- ble elements, z As moving images or even plastically-acting images are generated.
- the optically variable elements For the mass production of the optically variable elements, it is customary to produce so-called "master structures" which have the respective phase information of the optically variable element in the form of a spatial relief structure, which is usually a glass, plastic, metal or semiconductor substrate
- master structures which have the respective phase information of the optically variable element in the form of a spatial relief structure, which is usually a glass, plastic, metal or semiconductor substrate
- embossing and removing the relief structure by embossing and removing the relief structure, arbitrarily shaped embossing tools can be produced, with the aid of which the diffraction structures represented by the relief structure can be enlarged in size
- the relief structures can be generated either by holographic exposure or by electron beam lithography.
- resist is to be understood in this context as a radiation-sensitive lacquer, whereby the term “photoresist” refers to photosensitivity and the term “e-beam resist” to sensitivity to the exposure to an electron beam, although resist types are also known , which are sensitive to both electromagnetic radiation, in particular light, as well as for the irradiation with electrons. Chemically, the resist is a film-forming material whose solubility behavior changes under light or particle radiation.
- “Positive resist” refers to resist materials which readily become soluble under irradiation by degradation or conversion of functional groups
- Resist materials are referred to as "negative resist", which become sparingly soluble or insoluble under irradiation by crosslinking or polymerization, as a result of which the unexposed areas are dissolved away during further treatment, while the irradiated areas remain stationary.
- the relief structures that represent the diffraction structure of an optically variable element in the Generally have flat sloping edges or flanks with a defined slope.
- the invention is based on the abe to specify a method by which a relief structure with flat flanks or flanks can be produced in a simple manner for electron beam lithography, in particular for generating hologram-like structures in a resist layer , Furthermore, the invention has for its object to provide a suitable for carrying out the process resist substrate and a resist master for stamping tools.
- the invention is based on the finding that the range of action of this additional exposure depends on the electron beam energy and the conductive material used and that by appropriate choice of the exposure parameters and the conductive material of the Proximity Eff eective targeted for the generation of inclined flanks, as they are for the Production of Resistmastern are necessary, can be used.
- the material of the resist layer and of the conductive layer and the exposure parameters are matched to one another such that the resist layer is also exposed outside the region exposed to the electron beam so that the flanks of the relief structure receive an inclined form. It is to be considered as an indication that flatter flanks are due to a higher atomic number of the metal contained in the conductive layer, a softer gradation of Resist, a higher acceleration voltage of the electrons and a blurred and larger beam cross-section can be generated.
- This method has the advantage that it can be performed in a much shorter time compared to conventional methods for producing a substrate having a resist layer in the form of a relief structure, since only a single exposure step is required. In addition, the exposure time is reduced in addition, since the total effective radiation dose is increased by the secondary electrodes. In addition, a wide range of resist types can be used for the process. The method is thus not dependent on the use of insensitive resist materials as the known methods. The inclination of the flanks of the relief structure also leads to a good release behavior of the embossing lacquer from the embossing molds, which are shaped by the relief structure.
- metal layers or metal alloy layers of tungsten, gold, palladium, chromium, aluminum or mixtures of these metals are preferably used because of their good processability.
- High scattering and secondary electron emission is achieved, for example, with tungsten, gold or a gold-palladium alloy. Since the proximity effect is greater, the higher the atomic number of the chemical elements used, the use of metals with high atomic numbers, in particular greater than 50, is preferred.
- the conductive layer may form the carrier substrate for the resist layer or may be applied as a separate layer. In some embodiments, it may also be necessary to remove the conductive layer after the electron beam exposure again. For this purpose, appropriate solvents are used.
- the electron beam exposure is carried out with Elek- tronenstahlenergy from 0.1 to 100 keV, preferably in the range of 1 to 50 keV
- the conductive layer is disposed between the resist layer and the substrate.
- a negative resist is used, so that resist areas which are adjacent to the conductive layer and adjacent to the directly exposed area are also exposed by the backscattering of the primary electrons and the secondary electron emission.
- the unexposed areas are removed and only the areas directly exposed to the electron beam and by the proximity effect remain on the substrate.
- a positive resist is used, which on a surface facing away from the substrate with the conductive
- the resist areas adjacent to the conductive layer and located outside the directly exposed area are also exposed.
- the exposed areas are loosened and only the unexposed areas, which are exposed neither directly nor by the proximity effect, remain on the substrate.
- the electron beam exposure can be combined with an optical exposure in the form of electromagnetic radiation.
- a positive resist is applied to the substrate, which can be exposed to both electromagnetic radiation and an electron beam.
- an optical exposure takes place.
- the areas provided for exposure to the electron beam are covered during the optical exposure by means of an opaque mask.
- the conductive layer is applied to the not yet developed positive resist.
- the areas previously covered by an opaque mask are then exposed by means of an electron beam, the forward scattering of the beam electrons and the emission of the secondary electrons from the conductive layer effecting the exposure of the resist beneath the conductive layer and adjacent the area directly exposed to the electron beam.
- the conductive layer is then removed with a suitable solvent and the positive resist developed.
- a negative resist is used.
- the negative resist in the beam direction before the conductive
- a light radiation absorbing layer may be provided between the resist layer and the conductive layer.
- different resist layers may be arranged one behind the other in the beam direction.
- a first resist layer which can be exposed by means of electromagnetic radiation in the beam direction in front of a second resist layer which can be exposed with an electron beam.
- the conductive layer can then be arranged between the two resist layers or in the beam direction behind the second resist layer which can be exposed with an electron beam.
- the different embodiments of the method serve to produce a substrate having a relief-like structured resist layer is provided.
- the substrate produced by the process according to the invention is galvanically molded after development and multiplied by known processes in order to produce an embossing stamp, in particular an embossing cylinder such as banknotes, checks, identity cards or the like are also used in the field of product assurance embossed diffractive structure elements are often used.
- FIGS. 1A and B show the exposure of a negative-resist coated substrate to an electron beam and a cross-section through the substrate after development;
- FIGS. 2A to C show a cross section through a substrate provided with a negative resist, which is exposed by means of an electron beam with a different dose of radiation;
- Figure 3 A to C the substrate of Figures 2A to C after development.
- FIGS. 6A to C show successive method steps of a method with a combination of an optical exposure and a further exposure by means of an electron beam;
- FIGS. 7A to 7C show successive method steps of another
- FIG. 9 shows a modified embodiment of a resist substrate
- FIG. 10 embodiment in which the conductive layer is applied to a separate carrier.
- FIG. 1A shows a cross section of a substrate 1 onto which a conductive layer 2 made of a conductive material is applied.
- the conductive layer 2 may be made of, for example, a metal or a metal alloy or a conductive polymer.
- a resist layer 3 made of a negative resist. Since the negative resist 3 is generally not conductive itself, the conductive layer 2 serves to dissipate the electrons striking an electron beam 4.
- the conductive layer 2 can be dispensed with if the substrate 1 itself is sufficiently conductive.
- an exposure region 6 forms around a target area 5 impinged by the electron beam 4, through which an area of the negative adjacent to the target area 5 Resist 3 is exposed.
- the extent of the exposure area 6 is determined by the materials used, the electron acceleration voltage and by the beam dose, which in turn depends on the intensity and the writing speed of the electron beam 4.
- This scattering of the primary electrons and the emission of the secondary electrons are referred to as the proximity effect.
- the proximity effect is all the more pronounced the higher the atomic number of the material used for the conductive layer 2.
- metals with a high atomic number for.
- tungsten or gold used.
- tungsten or gold is a gold-palladium alloy, which leads to more uniform conductive layers 2 as pure gold.
- chromium or aluminum are also suitable as elements for the conductive layer 2.
- the conductive layer, the resist and the beam data are matched to one another in such a way that, due to proximity effects, exposure takes place to the desired extent in the area adjacent to the incident beam.
- the relief profile 7 has a slope angle 8, which is significantly smaller than 90 °. Erfindungsge- In principle, all flank angles of less than 90 ° can be produced, and angles between approximately 30 ° and 89 ° are preferred.
- the procedure is, for example, as follows:
- a quartz plate having a thickness of about 2 mm is used as the substrate 1.
- An approximately 80 nm thick, serving as a conductive layer 2 AuPd layer is vapor-deposited on this.
- the negative resist 3 is spun from an e-beam negative resist material with 250 nm thickness ("spin coating") and cured ("bake").
- the exposure of the negative resist 3 is effected by means of the electron beam 4 whose electrons have been accelerated to 5 keV.
- the electron beam 4 is guided along the lines provided for the diffraction grating and exposes the resist layer 3 in the region of these lines.
- a diffraction grating is inscribed in the resist layer 3 by the electron beam 4.
- the diffraction grating generally covers the area of a grid field whose outline or contour is predetermined by the design of the grid image.
- the distance between the individual tracks of the electron beam 4 is typically 1 micrometer.
- FIGS. 2A to 2C show the extent of the exposure areas 6 as a function of the radiation dose.
- FIG. 2A shows the extent of the exposure area 6 with a low dose of radiation
- FIG. 2B with an average dose of radiation
- FIG. 2C with a high dose of radiation.
- the optimal dose of radiation is determined by tests depending on the selected resist material and proximity layer material.
- FIGS. 3A to 3C show the relief structures 7 which result after the development of the negative resist 3 from FIGS. 2A to 2C. With a small dose of radiation, the relief structure 7 only has individual isolated elevations 9 after development.
- the mean jet dose shown in FIG. 2B leads to the relief structure 7 shown in FIG. 3B with a nearly sinusoidal cross-sectional profile.
- an excessively high radiation dose leads to the relief structure 7 shown in FIG. 3C, in which case the developed negative resist layer 3 has only isolated recesses 10.
- the relief structure 7 according to FIG. 3B is particularly advantageous since the embossing tools shaped by this relief structure exhibit the best detachment behavior during embossing and because the embossed material has a high degree of brilliance in a wide viewing angle range as a diffraction grating.
- the method can also be carried out with a positive resist.
- a positive resist Such an embodiment is shown in Figs. 4A to 4C.
- an approximately 2 mm thick quartz glass plate is used as the substrate 1.
- a positive resist 11 made of E-beam positive resist material of 250 nm thickness is applied and cured.
- an approximately 40 nm thick conductive layer 12 is vapor-deposited.
- the exposure takes place with the aid of the electron beam 4, whose electrons have been accelerated to an energy of 5 keV.
- the writing operation takes place as in the embodiment shown in FIGS. 2A to 2C and FIGS. 3A to 3C.
- the grid lines are typically written at a distance of about 1 ⁇ m.
- the exposure region 6 Due to the forward scattering of the primary electrons incident on the electron beam 4 and the emission of the secondary electrons in the dissipation layer 12, the exposure region 6 also comes in the region of the positive Resist layer 11 to lie.
- the beam dose determined by current intensity and writing speed of the electron beam 4 is again optimized in experiments.
- the conductive layer 12 may need to be removed after exposure.
- suitable solvents are known to those skilled in the art.
- gold for example, the TFA type gold etching solution from Transene Co., Rowel Ma is suitable.
- An etching solution suitable for chromium is an etching solution of the type TR-14 of Cyantek Corp., 3055 Osgood Ct., Fermont CA 94548.
- FIGS. 5A to 5C show the cross-sectional profile of the positive resist layer 11 after development.
- the cross-sectional profile of the positive resist layer shown in Fig. 5A is the result of the small dose of radiation of the electron beam 4 of Fig. 4A.
- the cross-sectional profiles of the positive resist layer 11 shown in FIGS. 5B and 5C result due to the radiation dose of the electron beam 4 shown in FIGS. 4B and 4C.
- the exposure region extends only slightly beyond the surface of the positive resist layer 11 into the positive resist layer 11. Accordingly, after the form
- the positive resist layer 11 Only develop individual isolated recesses 13 in the surface of the positive resist layer 11. On the other hand, with a medium dose of radiation, the positive resist layer 11 exhibits a nearly sinusoidal profile after development, which is particularly desirable, since the embossing lacquer easily separates from the embossing patterns produced by the positive resist 11 and the finished variable optical elements over a wide viewing angle range have high optical brilliance. If the jet dose is chosen too high, the isolated elevations 14 shown in FIG. 5C result. It should be noted that after exposure to the electron beam 4 and prior to the development of the positive resist 11, the drainage layer 12 must be dissolved by means of a suitable etching solution.
- the dissolution of the dissipation layer 12 can be avoided if the dissipation layer 12 is arranged on a separate foil 40, as shown in FIG.
- the film 40 or the dissipation layer 12 is brought into close contact with the resist layer during the exposure and can then be easily removed by removal.
- FIGS. 6A to 6C show successive method steps of such a method.
- an approximately 250 nm thick positive resist 15 is first applied, which can be exposed both to blue light and to an electron beam.
- a positive resist is, for example, the resist material AZ 5206 from Hoechst.
- a holographic exposure is then effected by superimposing spatially extended, uniformly coherent wave fields 16 in the positive resist 15.
- the areas of the positive resist 15 to be later exposed to the electron beam 4 are masked by means of an opaque mask 17 located on the underside of a transparent film 18.
- the technique of holographic exposure as such is known to those skilled in the art.
- the holographic exposure generates in the positive resist 15 latent grid structures with sinusoidal profile, which are shown in Figures 6 A and 6B respectively by a dashed line.
- the as yet undeveloped positive resist 15 is vapor-deposited with a preferably 20 to 100 nm thick dissipation layer 19 made of gold.
- the regions of the positive resist 15 covered with the mask 17 during the holographic exposure are subsequently exposed using the electron beam 4 according to FIG. 6B.
- the exposure using the electron beam 4 can take place such that to be filled by a contour or an outline limited grating fields ⁇ a grating image having different diffraction gratings. Due to the scattering of the primary electrons and the emission of the secondary electrons in the conductive layer 19, the exposure regions 6 extend so far into the positive resist layer 19 that after development, the grating lines written by the electron beam 4 also receive the sine profile shown in FIG. 6C. However, before the development of the positive resist layer 15, the drain layer 19 must be removed by using an etching solution.
- FIGS. 7A to 7C show method steps of such a method.
- a dissipation layer 20, which is covered with an antireflection layer 21, is applied to the substrate 1.
- a negative resist 22 is applied, which can be exposed both with blue light and with an electron beam.
- the exposure time for the exposure to light is tronenstrahl 4 provided region of the negative resist layer 22 covered by the mask 17.
- FIG. 7A This process step is shown in FIG. 7A.
- the antireflection layer 21 serves to prevent reflections on the metallic dissipation layer 20, which could disturb the superposition of the wave fields 16 in the region of the negative resist 22.
- the result of the holographic exposure is the latent diffraction grating drawn in dashed lines in FIGS. 7A and 7B.
- the substrate according to FIG. 7B is exposed to the electron beam 4, the backscattered primary electrons and the emission of the secondary electrons causing the exposure area 6 to extend into the negative resist 22.
- the grid lines shown in cross section in FIG. 7C with a sinusoidal grating profile result.
- FIGS. 6 and 7 are used in particular when an image is to be produced with a motif arranged in front of a background.
- the background can be generated with the holographic exposure while the grids of the subject are formed by the electron beam 4.
- the electron beam recording method according to the present invention may be combined with any other exposure and recording methods. This applies to all described embodiments.
- the embodiment of a combined method illustrated in FIGS. 6A to 6C offers the advantage that the positive resist generally has greater sensitivity than a negative resist.
- the conductive layer must be removed prior to development. This method step is omitted in the embodiment of a combined method with a negative resist illustrated in FIGS. 7A to 7C.
- the negative resist 22 or the positive resist 15 need not be made of a uniform resist material. It is also conceivable to provide for the positive resist 15 and the negative resist 22 regions of different resist materials, which may also have different thickness.
- FIGS. 8A to 8E show an exemplary embodiment of a method in which a conductive layer 23 is first applied to the substrate 1.
- a negative resist 24 which is largely insensitive to optical radiation.
- the negative resist 24 is darkened, so that optical radiation is absorbed into the negative resist 24.
- the negative resist 24 is suitable for exposure to the electron beam 4.
- the negative resist 24 has a desired layer thickness of, for example, 200 nm for electron beam exposure.
- a 400 nm thick positive resist 25 is applied, which has a high sensitivity for optical radiation.
- the substrate shown in Fig. 8 A is thus ready for exposure.
- the order of the following exposure steps is arbitrary.
- the optical exposure is started.
- An area provided for the optical exposure is holographically exposed to electromagnetic radiation 16, eg a laser.
- the area 26 thus exposed contains the latent diffraction grating, which is indicated by a dashed sine curve in FIG. 8B.
- the negative resist 24 lying in the area 26 is not damaged because of its optical insensitivity and serves as an absorption layer in order to avoid undesired light spots.
- the area 26 which is optically exposed in this way is now covered by a mask 27 and an area 28 provided for the electron beam exposure is first preexposed with blue light 29 over the whole area in order to render the positive resist 25 in the area 28 detachable.
- the action of the blue light 29 has egen the light resistance of the negative resist 24 no effect on lying in the area 28 negative resist 24th
- the exposure to the electron beam 4 takes place.
- the backscattered primary electrons and the emission of the secondary electrons expose the negative resist 24 to the desired diffraction grating.
- the damage caused by the electron beam 4 in the positive resist 25 is irrelevant since the positive resist 25 in the region 28 is ultimately removed.
- the exposure is hereby completed.
- FIG. 8E shows Valley profiles, which are shown in Fig. 8E in cross section.
- a holographic image is now present in the region 26, and in the region 28 the negative resist 24 forms a diffraction grating with a sinusoidal cross-sectional profile.
- Fig. 9 shows a modified layer structure, which however is treated the same as the layer structure of Fig. 8A.
- a positive resist 30 is applied to the substrate 1, which is covered with a conductive layer 31.
- a positive or negative resist 32 which is sensitive to optical light.
- an antireflection layer 33 is disposed between the resist layer 32 and the conductive layer 31, an antireflection layer 33 is disposed.
- a relief structure as shown in FIG. 8E can be produced by exposing the resist layer 32 by means of electromagnetic radiation and the resist layer 30 by means of the electron beam 4.
- the relief structures 7 produced by exposure and development can be processed as resist masters in the usual way as in optical holography.
- a thin layer of silver is applied by vapor deposition or chemical precipitation, and a nickel impression is taken in the ceramic bath.
- the Nickelabf orm may be duplicated and used as an embossing stamp for embossing a recuperge für.
- the embossed layer is finally transferred to the final substrate, for example a banknote, credit card or packaging material, with or without a shiny metallic reflective background layer.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Structural Engineering (AREA)
- Architecture (AREA)
- Theoretical Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Diffracting Gratings Or Hologram Optical Elements (AREA)
- Electron Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE10308317 | 2003-02-26 | ||
DE10308317A DE10308317A1 (en) | 2003-02-26 | 2003-02-26 | Process for producing a resist substrate |
PCT/EP2004/001817 WO2004077161A2 (en) | 2003-02-26 | 2004-02-24 | Method for producing resist substrates |
Publications (1)
Publication Number | Publication Date |
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EP1599764A2 true EP1599764A2 (en) | 2005-11-30 |
Family
ID=32841923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP04713886A Withdrawn EP1599764A2 (en) | 2003-02-26 | 2004-02-24 | Method for producing resist substrates |
Country Status (7)
Country | Link |
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US (1) | US7655381B2 (en) |
EP (1) | EP1599764A2 (en) |
CN (1) | CN1754128B (en) |
AU (1) | AU2004214638B2 (en) |
DE (1) | DE10308317A1 (en) |
RU (1) | RU2334261C2 (en) |
WO (1) | WO2004077161A2 (en) |
Families Citing this family (3)
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RU2462784C1 (en) * | 2011-03-31 | 2012-09-27 | Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный электротехнический университет "ЛЭТИ" | Electron beam lithography |
US9177817B2 (en) * | 2011-08-23 | 2015-11-03 | The Research Foundation For The State University Of New York | Methods for fabricating three-dimensional nano-scale structures and devices |
CN105655233A (en) * | 2014-12-02 | 2016-06-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of submicron double-step pattern |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US3961102A (en) | 1974-09-13 | 1976-06-01 | Cornwell Research Foundation, Inc. | Scanning electron microscope fabrication of optical gratings |
JPS57162331A (en) * | 1981-03-31 | 1982-10-06 | Fujitsu Ltd | Forming method for wiring pattern |
JPS58124230A (en) * | 1982-01-20 | 1983-07-23 | Matsushita Electric Ind Co Ltd | Forming method for ultrafine pattern |
JPS62235305A (en) * | 1986-04-04 | 1987-10-15 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of high-molecular-weight acrylic polymer |
JP2938920B2 (en) * | 1990-01-31 | 1999-08-25 | 住友精化株式会社 | Method for producing water absorbent resin |
JP3391763B2 (en) * | 2000-03-03 | 2003-03-31 | 沖電気工業株式会社 | Manufacturing method of mask |
JP3686573B2 (en) | 2000-05-12 | 2005-08-24 | パイオニア株式会社 | Stamper forming electrode material and stamper forming thin film |
-
2003
- 2003-02-26 DE DE10308317A patent/DE10308317A1/en not_active Withdrawn
-
2004
- 2004-02-24 RU RU2005129551/04A patent/RU2334261C2/en not_active IP Right Cessation
- 2004-02-24 US US10/545,261 patent/US7655381B2/en not_active Expired - Fee Related
- 2004-02-24 CN CN2004800050715A patent/CN1754128B/en not_active Expired - Fee Related
- 2004-02-24 AU AU2004214638A patent/AU2004214638B2/en not_active Ceased
- 2004-02-24 EP EP04713886A patent/EP1599764A2/en not_active Withdrawn
- 2004-02-24 WO PCT/EP2004/001817 patent/WO2004077161A2/en active Application Filing
Non-Patent Citations (2)
Title |
---|
DATABASE INSPEC [online] THE INSTITUTION OF ELECTRICAL ENGINEERS, STEVENAGE, GB; 1995, WELLS G M ET AL: "X-ray mask fabrication process", Database accession no. 5147491 * |
PHOTOMASK AND X-RAY MASK TECHNOLOGY II 20-21 APRIL 1995 KAWASAKI CITY, JAPAN, vol. 2512, PROCEEDINGS OF THE SPIE - THE INTERNATIONAL SOCIETY FOR OPTICAL ENGINEERING SPIE-INT. SOC. OPT. ENG. USA, pages 167 - 171, ISSN: 0277-786X * |
Also Published As
Publication number | Publication date |
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WO2004077161A2 (en) | 2004-09-10 |
AU2004214638B2 (en) | 2009-07-23 |
CN1754128A (en) | 2006-03-29 |
WO2004077161A3 (en) | 2005-01-27 |
US7655381B2 (en) | 2010-02-02 |
DE10308317A1 (en) | 2004-09-09 |
US20060257583A1 (en) | 2006-11-16 |
CN1754128B (en) | 2011-09-28 |
AU2004214638A1 (en) | 2004-09-10 |
RU2005129551A (en) | 2007-04-20 |
RU2334261C2 (en) | 2008-09-20 |
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